Nb/NbCr_2合金表面硅化物涂层的高温抗氧化性能
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摘要
用扩散渗法在Nb/NbCr2合金表面制备硅化物涂层,研究了基体合金和涂层在1250℃的氧化行为。结果表明:在Nb/NbCr2合金表面渗Si所得硅化物涂层由(Nb,Cr)Si2和(Cr,Nb)Si2两相组成,过渡层为(Nb,Cr)5Si3,涂层的生长动力学服从抛物线规律。基体合金在1250℃氧化形成的氧化膜为Nb2O5和CrNbO4交替分布的疏松组织,与基体有剥离现象。渗Si涂层在1250℃氧化形成的氧化膜较为致密完整,与残留涂层结合良好,为SiO2和CrNbO4混合氧化膜,改善了合金的高温抗氧化性能。
Silicide coatings on Nb/NbCr2 alloy were prepared by pack cementation method. The oxidation behavior of the bare- and coated- alloy was examined by isothermal test at 1250 ℃ in static air.The results show that the silicide coatings are composed of(Nb, Cr)Si2and(Cr, Nb)Si2phases. There exist a transitional layer of(Nb, Cr)5Si3in between the main coating and substrate. The coating growth kinetics at 1250℃ fits to parabolic law. The oxidation of Nb/NbCr2 alloy resulted in alternate layers of Nb2O5 and Cr Nb O4 with porous structure, which was wrinkling even spalling off after oxidation. The scale formed on the silicide coating after oxidation at 1250℃ was mainly composed of Si O2 and Cr Nb O4. The scale was relatively dense and had a good bond with the residual coating, thus showing an excellent oxidation resistance.
Silicide coatings on Nb/NbCr2 alloy were prepared by pack cementation method. The oxidation behavior of the bare- and coated- alloy was examined by isothermal test at 1250 ℃ in static air.The results show that the silicide coatings are composed of(Nb, Cr)Si2and(Cr, Nb)Si2phases. There exist a transitional layer of(Nb, Cr)5Si3in between the main coating and substrate. The coating growth kinetics at 1250℃ fits to parabolic law. The oxidation of Nb/NbCr2 alloy resulted in alternate layers of Nb2O5 and Cr Nb O4 with porous structure, which was wrinkling even spalling off after oxidation. The scale formed on the silicide coating after oxidation at 1250℃ was mainly composed of Si O2 and Cr Nb O4. The scale was relatively dense and had a good bond with the residual coating, thus showing an excellent oxidation resistance.
引文
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2 ZHENG Haizhong,LU Shiqian,XIAO Xuan,LI Xin,WANG Kelu,DONG Xianjuan,Research progress on brittleness of Laves phase Nb Cr2compounds at ambient temperature,Rare Metal Mater.Eng.,36 (1),178(2007)(郑海忠,鲁世强,肖旋,李鑫,王克鲁,董显娟,Laves相Nb Cr2室温脆性的研究进展,稀有金属材料与工程,36(1),178(2007))
3 K.S.Chan,Alloying effects on fracture mechanisms in Nb-based intermetallic in-situ composites,Mat.Sci.Eng.A,329,513(2002)
4 ZHANG Mingjun,GUO Xiping,Microstructure and properties of Nb-Cr based multi-element alloy,Rare Metal Mater.Eng.,37(6),984 (2008)(张明军,郭喜平,Nb-Cr系多元合金的组织和性能,稀有金属材料与工程,37(6),984(2008))
5 XIAO Xuan,LU Shiqiang,MA Yanqing,HU Ping,HUANG Minggang,NIE Xiaowu,Effect of MA and soft second phase on microstructures and properties of Cr/Cr2Nb composite materials,Rare Metal Mater.Eng.,37(1),119(2008)(肖璇,鲁世强,马燕青,胡平,黄铭刚,聂小武,MA和软第二相对Cr/Cr2Nb复合材料组织与性能的影响,稀有金属材料与工程,37(1),119(2008))
6 ZHENG Haizhong,LU Shiqian,ZHU Jianye,ZHOU Wei,Effects of Al on the microstructure and fracture toughness of Nb Cr2alloys,Rare Metal Mater.Eng.,38(1),80(2009)(郑海忠,鲁世强,祝建业,周伟,合金元素Al对Laves相Nb Cr2显微组织及断裂韧性的影响,稀有金属材料与工程,38(1),80(2009))
7 ZHENG Haizhong,LU Shiqian,WANG Kelu,SU Qian,NIE Xiaowu,Progress in studies on high temperature oxidation resistance of Laves phase Nb Cr2compounds,Corr.Sci.Prot.Technol.,19 (6),427(2007)(郑海忠,鲁世强,王克鲁,苏倩,聂小武,Laves相Nb Cr2高温抗氧化性研究的进展,腐蚀科学与防护技术,19(6),427(2007))
8 M.P.Brady,J.H.Zhu,C.T.Liu,P.F.Tortorelli,L.R.Walker,Oxidation resistance and mechanical properties of Laves phase reinforced Cr in-situ composites,Intermetallics,8(9-11),1111(2000)
9 M.P.Brady,P.F.Tortorelli,L.R.Walker,Water vapor and oxygen/sulfur-impurity effects on oxidation and nitridation in single-and two-phase Cr-Nb alloys,Oxid.Met.,58(3/4),297(2002)
10 T.Ohta,Y.Nakagawa,Y.Kaneno,H.Inoue,T.Takasugi,Microstructures and mechanical properties of Nb Cr2and Zr Cr2Laves phase alloys prepared by powder metallurgy,J.Mater.Sci.,38(4),657(2003)
11 ZHENG Haizhong,LU Shiqian,Effect of multiple elements Al,Si and Y on high temperature oxidation of Cr-20Nb alloys,Rare Metal Mater.Eng.,40(3),433(2011)(郑海忠,鲁世强,Al,Si及Y多元合金化对Cr-20Nb合金高温氧化行为的影响,稀有金属材料与工程,40(3),433(2011))
12 H.Z.Zheng,S.Q.Lu,J.Y.Zhu,G.M.Liu,Effect of Al additions on the oxidation behavior of Laves phase Nb Cr2alloys at 1373 K and 1473 K,Int.J.Refr.Metals Hard Mater.,27(3),659(2009)
13 S.Q.Lu,H.Z.Zheng,L.P.Deng,J.Yao,Effect of silicon on the fracture toughness and oxidation behavior of hot pressed Nb Cr2alloys,Mater.Des.,51,432(2013)
14 ZHENG Haizhong,LU Shiqiang,Effects of grain refinement on high temperature oxidation behavior of Cr-25Nb alloys,Rare Metal Mater.Eng.,39(10),1082(2010)(郑海忠,鲁世强,晶粒细化对Cr-25Nb合金高温氧化行为的影响,稀有金属材料与工程,39(10),1082(2010))
15 H.Z.Zheng,S.Q.Lu,Y.Huang,Influence of grain size on the oxidation behavior of Nb Cr2alloys at 950-1200oC,Corros Sci,51(2),434(2009)
16 H.Z.Zheng,S.Q.Lu,Q.Su,F.J.Quan,Study on scaling of mechanically alloyed and hot pressed Nb Cr2Laves phase at 1200oC in air,Int.J.Refr.Metals Hard Mater.,26(1),1(2008)
17 ZHENG Haizhong,LU Shiqian,HUANG Yi,Effect of mechanical alloying on oxidation behavior at 1100℃of Laves phase Nb Cr2alloys by hot pressing synthesis,Rare Metal Mater.Eng.,38(10),1026(2009)(郑海忠,鲁世强,黄毅,机械合金化对热压合成Laves相Nb Cr2合金1100℃氧化行为的影响,稀有金属材料与工程,38(10),1026(2009))
18 B.P.Bewlay,M.R.Jackson,The effect of Hf and Ti additions on microstructure and properties of Cr2Nb–Nb in situ composites,J.Mater.Res.,11(8),1917(1996)
19 B.P.Bewlay,H.A.Lipsitt,M.R.Jackson,W.J.Reeder,J.A.Sutliff,Solidification processing of high temperature intermetallic eutectic-based alloys,Mat.Sci.Eng.A,192,534(1995)
20 N.David,Y.Cartigny,T.Belmonte,J.M.Fiorani,M.Vilasi,Thermodynamic description of the Cr-Nb-Si isothermal section at 1473K,Intermetallics,14(4),464(2006)
21 LI Ming,SONG Lixin,LE Jun,SONG Xueping,GUO Zhancheng,Microstructure and mechanism of pack siliconizing on niobium,J.Inorg.Mater.,20(3),764(2005)(李明,宋力昕,乐军,宋学平,郭占成,铌表面固体粉末包埋渗硅研究,无机材料学报,20(3),764(2005))
22 Y.Q.Qiao,X.P.Guo,Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process,Appl.Surf.Sci.,256(24),7462(2010)
23 ZHAO Luxiang,GUO Xiping,JIANG Yuanyuan,Preparation and structural formation of oxidation-resistant silicide coatings on Nbbased alloy by pack cementation technique,Chin.J.Nonferrous Metal.,17(4),576(2007)(赵陆翔,郭喜平,姜嫄嫄,铌基合金包埋渗法制备抗氧化硅化物涂层及其组织形成,中国有色金属学报,17(4),576(2007))
24 B.V.Cockeram,Growth and oxidation resistance of boron-modified and germanium-doped silicide diffusion coatings formed by the halide-activated pack cementation method,Surf.Coat.Technol.,76(1),20(1995)
25 Y.Du,J.C.Schuster,Experimental reinvestigation of the Cr Si-Si partial system and update of the thermodynamic description of the entire Cr-Si system,J.Phase Equilib.,21(3),281(2000)
26 P.Zhang,X.P.Guo,Y and Al modified silicide coatings on an NbTi-Si based ultrahigh temperature alloy prepared by pack cementation process,Surf.Coat.Technol.,206(2),446(2011)
27 LI Xuan,GUO Xiping,Effects of activators on formation of Si-ZrY co-deposition coatings on Nb-Ti-Si-Cr base ultrahigh temperature alloy,Acta Metall.Sin.,48(11),1394(2012)(李轩,郭喜平,催化剂对Nb-Ti-Si-Cr基超高温合金表面Si-Zr-Y共渗层组织的影响,金属学报,48(11),1394(2012))
28 D.J.Derry,G.D.Lees,The oxidation behaviour of a niobium-chromium-nickel alloy,Corros.Sci.,16(4),219(1976)
2 ZHENG Haizhong,LU Shiqian,XIAO Xuan,LI Xin,WANG Kelu,DONG Xianjuan,Research progress on brittleness of Laves phase Nb Cr2compounds at ambient temperature,Rare Metal Mater.Eng.,36 (1),178(2007)(郑海忠,鲁世强,肖旋,李鑫,王克鲁,董显娟,Laves相Nb Cr2室温脆性的研究进展,稀有金属材料与工程,36(1),178(2007))
3 K.S.Chan,Alloying effects on fracture mechanisms in Nb-based intermetallic in-situ composites,Mat.Sci.Eng.A,329,513(2002)
4 ZHANG Mingjun,GUO Xiping,Microstructure and properties of Nb-Cr based multi-element alloy,Rare Metal Mater.Eng.,37(6),984 (2008)(张明军,郭喜平,Nb-Cr系多元合金的组织和性能,稀有金属材料与工程,37(6),984(2008))
5 XIAO Xuan,LU Shiqiang,MA Yanqing,HU Ping,HUANG Minggang,NIE Xiaowu,Effect of MA and soft second phase on microstructures and properties of Cr/Cr2Nb composite materials,Rare Metal Mater.Eng.,37(1),119(2008)(肖璇,鲁世强,马燕青,胡平,黄铭刚,聂小武,MA和软第二相对Cr/Cr2Nb复合材料组织与性能的影响,稀有金属材料与工程,37(1),119(2008))
6 ZHENG Haizhong,LU Shiqian,ZHU Jianye,ZHOU Wei,Effects of Al on the microstructure and fracture toughness of Nb Cr2alloys,Rare Metal Mater.Eng.,38(1),80(2009)(郑海忠,鲁世强,祝建业,周伟,合金元素Al对Laves相Nb Cr2显微组织及断裂韧性的影响,稀有金属材料与工程,38(1),80(2009))
7 ZHENG Haizhong,LU Shiqian,WANG Kelu,SU Qian,NIE Xiaowu,Progress in studies on high temperature oxidation resistance of Laves phase Nb Cr2compounds,Corr.Sci.Prot.Technol.,19 (6),427(2007)(郑海忠,鲁世强,王克鲁,苏倩,聂小武,Laves相Nb Cr2高温抗氧化性研究的进展,腐蚀科学与防护技术,19(6),427(2007))
8 M.P.Brady,J.H.Zhu,C.T.Liu,P.F.Tortorelli,L.R.Walker,Oxidation resistance and mechanical properties of Laves phase reinforced Cr in-situ composites,Intermetallics,8(9-11),1111(2000)
9 M.P.Brady,P.F.Tortorelli,L.R.Walker,Water vapor and oxygen/sulfur-impurity effects on oxidation and nitridation in single-and two-phase Cr-Nb alloys,Oxid.Met.,58(3/4),297(2002)
10 T.Ohta,Y.Nakagawa,Y.Kaneno,H.Inoue,T.Takasugi,Microstructures and mechanical properties of Nb Cr2and Zr Cr2Laves phase alloys prepared by powder metallurgy,J.Mater.Sci.,38(4),657(2003)
11 ZHENG Haizhong,LU Shiqian,Effect of multiple elements Al,Si and Y on high temperature oxidation of Cr-20Nb alloys,Rare Metal Mater.Eng.,40(3),433(2011)(郑海忠,鲁世强,Al,Si及Y多元合金化对Cr-20Nb合金高温氧化行为的影响,稀有金属材料与工程,40(3),433(2011))
12 H.Z.Zheng,S.Q.Lu,J.Y.Zhu,G.M.Liu,Effect of Al additions on the oxidation behavior of Laves phase Nb Cr2alloys at 1373 K and 1473 K,Int.J.Refr.Metals Hard Mater.,27(3),659(2009)
13 S.Q.Lu,H.Z.Zheng,L.P.Deng,J.Yao,Effect of silicon on the fracture toughness and oxidation behavior of hot pressed Nb Cr2alloys,Mater.Des.,51,432(2013)
14 ZHENG Haizhong,LU Shiqiang,Effects of grain refinement on high temperature oxidation behavior of Cr-25Nb alloys,Rare Metal Mater.Eng.,39(10),1082(2010)(郑海忠,鲁世强,晶粒细化对Cr-25Nb合金高温氧化行为的影响,稀有金属材料与工程,39(10),1082(2010))
15 H.Z.Zheng,S.Q.Lu,Y.Huang,Influence of grain size on the oxidation behavior of Nb Cr2alloys at 950-1200oC,Corros Sci,51(2),434(2009)
16 H.Z.Zheng,S.Q.Lu,Q.Su,F.J.Quan,Study on scaling of mechanically alloyed and hot pressed Nb Cr2Laves phase at 1200oC in air,Int.J.Refr.Metals Hard Mater.,26(1),1(2008)
17 ZHENG Haizhong,LU Shiqian,HUANG Yi,Effect of mechanical alloying on oxidation behavior at 1100℃of Laves phase Nb Cr2alloys by hot pressing synthesis,Rare Metal Mater.Eng.,38(10),1026(2009)(郑海忠,鲁世强,黄毅,机械合金化对热压合成Laves相Nb Cr2合金1100℃氧化行为的影响,稀有金属材料与工程,38(10),1026(2009))
18 B.P.Bewlay,M.R.Jackson,The effect of Hf and Ti additions on microstructure and properties of Cr2Nb–Nb in situ composites,J.Mater.Res.,11(8),1917(1996)
19 B.P.Bewlay,H.A.Lipsitt,M.R.Jackson,W.J.Reeder,J.A.Sutliff,Solidification processing of high temperature intermetallic eutectic-based alloys,Mat.Sci.Eng.A,192,534(1995)
20 N.David,Y.Cartigny,T.Belmonte,J.M.Fiorani,M.Vilasi,Thermodynamic description of the Cr-Nb-Si isothermal section at 1473K,Intermetallics,14(4),464(2006)
21 LI Ming,SONG Lixin,LE Jun,SONG Xueping,GUO Zhancheng,Microstructure and mechanism of pack siliconizing on niobium,J.Inorg.Mater.,20(3),764(2005)(李明,宋力昕,乐军,宋学平,郭占成,铌表面固体粉末包埋渗硅研究,无机材料学报,20(3),764(2005))
22 Y.Q.Qiao,X.P.Guo,Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process,Appl.Surf.Sci.,256(24),7462(2010)
23 ZHAO Luxiang,GUO Xiping,JIANG Yuanyuan,Preparation and structural formation of oxidation-resistant silicide coatings on Nbbased alloy by pack cementation technique,Chin.J.Nonferrous Metal.,17(4),576(2007)(赵陆翔,郭喜平,姜嫄嫄,铌基合金包埋渗法制备抗氧化硅化物涂层及其组织形成,中国有色金属学报,17(4),576(2007))
24 B.V.Cockeram,Growth and oxidation resistance of boron-modified and germanium-doped silicide diffusion coatings formed by the halide-activated pack cementation method,Surf.Coat.Technol.,76(1),20(1995)
25 Y.Du,J.C.Schuster,Experimental reinvestigation of the Cr Si-Si partial system and update of the thermodynamic description of the entire Cr-Si system,J.Phase Equilib.,21(3),281(2000)
26 P.Zhang,X.P.Guo,Y and Al modified silicide coatings on an NbTi-Si based ultrahigh temperature alloy prepared by pack cementation process,Surf.Coat.Technol.,206(2),446(2011)
27 LI Xuan,GUO Xiping,Effects of activators on formation of Si-ZrY co-deposition coatings on Nb-Ti-Si-Cr base ultrahigh temperature alloy,Acta Metall.Sin.,48(11),1394(2012)(李轩,郭喜平,催化剂对Nb-Ti-Si-Cr基超高温合金表面Si-Zr-Y共渗层组织的影响,金属学报,48(11),1394(2012))
28 D.J.Derry,G.D.Lees,The oxidation behaviour of a niobium-chromium-nickel alloy,Corros.Sci.,16(4),219(1976)